EP0288344B1 - Elektrochemisches Verfahren zur Rückgewinnung von metallischem Rhodium aus wässerigen Lösungen von gebrauchten Katalysatoren - Google Patents

Elektrochemisches Verfahren zur Rückgewinnung von metallischem Rhodium aus wässerigen Lösungen von gebrauchten Katalysatoren Download PDF

Info

Publication number
EP0288344B1
EP0288344B1 EP19880400716 EP88400716A EP0288344B1 EP 0288344 B1 EP0288344 B1 EP 0288344B1 EP 19880400716 EP19880400716 EP 19880400716 EP 88400716 A EP88400716 A EP 88400716A EP 0288344 B1 EP0288344 B1 EP 0288344B1
Authority
EP
European Patent Office
Prior art keywords
rhodium
cathode
process according
reference electrode
chosen
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
Application number
EP19880400716
Other languages
English (en)
French (fr)
Other versions
EP0288344A1 (de
Inventor
Marie-Céline Caude
Didier Morel
Jean-Pierre Pulicani
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhone Poulenc Sante SA
Original Assignee
Rhone Poulenc Sante SA
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhone Poulenc Sante SA filed Critical Rhone Poulenc Sante SA
Priority to AT88400716T priority Critical patent/ATE55422T1/de
Publication of EP0288344A1 publication Critical patent/EP0288344A1/de
Application granted granted Critical
Publication of EP0288344B1 publication Critical patent/EP0288344B1/de
Anticipated expiration legal-status Critical
Expired - Lifetime legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
    • C25C—PROCESSES FOR THE ELECTROLYTIC PRODUCTION, RECOVERY OR REFINING OF METALS; APPARATUS THEREFOR
    • C25C1/00—Electrolytic production, recovery or refining of metals by electrolysis of solutions
    • C25C1/20—Electrolytic production, recovery or refining of metals by electrolysis of solutions of noble metals
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Definitions

  • the present invention relates to an electrochemical process for recovering rhodium in metallic form from aqueous solutions of used catalysts.
  • Rhodium is a metal which is used as a catalyst, generally in the form of salts or complexes, to carry out numerous syntheses in organic chemistry.
  • Rhodium is a relatively rare metal with a high cost. It is particularly important to be able to recover it when the catalyst has lost its efficiency in order to be able to recycle it.
  • the selective addition of a compound having an active methylene group can be carried out on a terminal conjugated diene (European patent EP 44771), the addition of a cyclic secondary amine on a terminal conjugated diene (European patent EP 185,559) or else the selective alkylation of phenols (European patent application EP 161,132) or else the hydroformylation of olefins (FR 2,349,562).
  • a compound having an active methylene group such as a p-ketoester
  • the aqueous phase the pH of which is close to neutral, consists essentially of rhodium in the form of organometallic complexes, sulfonated phosphines and their degradation products (phosphine oxides), water, alcohol (methanol) used as a co-solvent and organic products (reagents and reaction products).
  • phosphine oxides organometallic complexes, sulfonated phosphines and their degradation products (phosphine oxides), water, alcohol (methanol) used as a co-solvent and organic products (reagents and reaction products).
  • the rhodium can be recovered in metallic form by electrochemical reduction of an aqueous solution of a water-soluble catalytic system, essentially containing a rhodium complex, mineral or organometallic, a sulphonated phosphine and its oxidized derivatives, residual organic products, solvents and mineral salts having previously undergone an appropriate treatment of oxidation and acidification.
  • the purpose of the oxidative treatment is to transform the residual trivalent phosphorus into pentavalent phosphorus and to oxidize the monovalent rhodium to trivalent rhodium, acidification being necessary for the rhodium to be in an electro-reducible form.
  • a concentrated solution is used, the volume of which represents approximately one third of the initial volume so as to have a rhodium concentration of between 1 and 5 g / liter.
  • the concentration is carried out by distillation, optionally under reduced pressure.
  • the oxidation of the spent catalyst solution is carried out using an agent having a strong oxidizing power preferably chosen from hypochlorites and chlorates of alkali metals, such as bleach, sodium chlorate. or potassium, operating at a temperature between 20 ° C and the reflux temperature of the reaction mixture.
  • an agent having a strong oxidizing power preferably chosen from hypochlorites and chlorates of alkali metals, such as bleach, sodium chlorate. or potassium, operating at a temperature between 20 ° C and the reflux temperature of the reaction mixture.
  • the oxidation is carried out at reflux temperature and is complete after a period which can range from 1 to 4 hours.
  • the oxidation can optionally be carried out using hydrogen peroxide.
  • the acidification is carried out by means of a strong acid so that the pH of the final solution is less than 3 and, preferably between 0 and 1. It is particularly advantageous to use a strong mineral acid chosen from hydrochloric, sulfuric, nitric and phosphoric acids. Preferably, the acidification is carried out at the reflux temperature of the reaction mixture, the heating being continued for 1 to 4 hours.
  • the electrolysis can be carried out continuously or discontinuously.
  • the electrolyser essentially consists of a cathode and an anode and possibly a diaphragm separating the cathode and anode compartments.
  • the electrolyser may further include a reference electrode such as a saturated calomel electrode.
  • the cathode is made of an electrically conductive material whose melting point must be low enough to allow the recovery of rhodium and which must be resistant to the aggressiveness of the environment. It is particularly advantageous to use a cathode made of stainless steel, mercury, copper or lead. Preferably, a copper or lead cathode is used.
  • the anode consists of an electrically conductive material which cannot be attacked under the conditions of electrolysis. It is particularly advantageous to use a graphite anode.
  • the anode compartment contains an electrolyte which, preferably, is the acid used to carry out the acidification during the pretreatment operation.
  • the current density at the start of the electrolysis is determined in such a way that the reduction of rhodium is maximum while limiting the reduction of the protons present in the strongly acid medium.
  • the current density is between 0.5 and 2 A / dm2. Due to the simultaneous reduction of part of the protons present in the medium, the electrical efficiency is not quantitative.
  • electrolysis is stopped after the passage of 50 Faradays per atom of rhodium.
  • the potential imposed on the cathode is chosen in such a way that the reduction of rhodium is maximum while limiting the reduction of the protons present in the strongly acid medium.
  • the potential of the cathode is between -0.25 and -0.55 volts relative to the reference electrode.
  • an electrolyser is generally used in which the anode, the cathode and the separating diaphragm are in vertical parallel planes.
  • the anode, the cathode and the separator diaphragm are in horizontal parallel planes.
  • an electrolyser comprising several anodes and cathodes arranged alternately and connected to the electrical supply by parallel circuits.
  • electrolysers to which are annexed devices such as heat exchangers, expansion vessels or devices for measuring temperature or pH.
  • the cathode (s) are removed from the solution then rinsed with water and optionally with an organic solvent such as methanol or acetone and finally dried.
  • the rhodium initially present in the solution is recovered with a yield greater than 80% in a solid form titrating more than 50% (w / w) of rhodium.
  • the metallic rhodium can be recovered either by melting the cathode or by melting the deposit obtained after scraping the cathode, the cathode being able in the latter case to be reused.
  • the rhodium in metallic form thus obtained can be refined, according to known techniques.
  • the rhodium obtained according to the process of the present invention can optionally be transformed into a salt (chloride, bromide, sulfate, nitrate) which can be used to prepare a complex useful as a catalyst in organic synthesis.
  • a salt chloride, bromide, sulfate, nitrate
  • the mixture is heated in a water bath at 80-82 ° C for 1 hour 20 minutes while stirring.
  • the precipitate which forms (0.152 g) is separated from the solution by filtration on sintered glass.
  • the precipitate contains 0.064% (w / w) of rhodium which is recovered by combustion according to known techniques.
  • 25 cm3 of the pretreated solution are introduced into the cathode compartment of an electrolysis cell, the two compartments of which are separated by a cationic membrane.
  • a copper cathode is introduced in the form of a 2.4 cm diameter disc.
  • the anode compartment contains 25 cm3 of hydrochloric acid N; we introduce a platinum grid of the same size.
  • the potential of the cathode is fixed at -0.3 volts relative to a reference calomel saturated electrode. The solution is stirred. After the passage of 359 coulombs, the electrolysis is stopped.
  • the copper cathode is covered with a gray deposit which is recovered by scraping, rinsed with water and acetone and then dried.
  • the initial solution contained 16.25 mg of rhodium and the final solution after electrolysis contains 2 mg.
  • the recovery rate is 88%.
  • the recovered deposit contains 46% rhodium and 39% copper.
  • the volume of the filtrate is brought to 500 cm3 by addition of water.
  • 250 cm3 of pre-treated solution are introduced into an electrolysis cell without a separating diaphragm.
  • a copper cathode and 2 graphite anodes with a surface of 25 cm 2 are plunged on either side and at equal distance from the cathode.
  • the voltage across the circuit is fixed at 2.66-2.9 volts.
  • the solution is constantly agitated. After passing 2530 coulombs, the electrolysis is stopped.
  • the copper cathode is covered with a gray deposit with a high rhodium content.
  • the initial solution contained 184 mg of rhodium and the final solution, after electrolysis, contains 25 mg.
  • the recovery rate is 86% ._

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Electrochemistry (AREA)
  • Materials Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Electrolytic Production Of Metals (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Catalysts (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)

Claims (9)

1. Verfahren zur Rückgewinnung von Rhodium in metallischer Form aus einer verbrauchten, wässrigen, katalytischen Lösung, die im wesentlichen einen Rhodiumkomplex, ein sulfoniertes Phosphin, und seine oxydierten Derivate, organische Rückstandsprodukte, Lösungsmittel und anorganische-Salze enthält, dadurch gekennzeichnet, daß man
-a) die wässrige Lösung mit einem Oxidationsmittel und einer starken Säure behandelt,
b) die so erhaltene Lösung einer elektrolytischen Reduktion unterwirft und dann
c) von der Kathode das abgelagerte metallische Rhodium entfernt.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß die wässrige Lösung des katalytischen Systems vor der Oxydations- und Säurebehandlung konzentriert wird.
3. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß die der Säurebehandlung folgende oder vorausgehende Oxydation mit einem Oxydationsmittel durchgeführt wird, das ausgewählt ist aus Alkalimetallhypochloriten und Alkalimetallchloraten.
4. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß die der Oxydation folgende oder vorausgehende Säurebehandlung mit einer starken anorganischen Säure ausgewählt aus Chlorwasserstoff-, Schwefel-, Salpeter- oder Phosphorsäure durchgeführt wird, um den pH-Wert unter 3 zu bringen.
5. Verfahren nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß die elektrolytische Reduktion in einem Elektrolyser mit einer Kathode, einer Anode und gegebenenfalls einer Bezugselektrode und/oder einer den Anoden- und Kathodenraum trennenden Membran durchgeführt wird, wobei die Kathode aus einem elektrisch leitenden Material mit niedrigem Schmelzpunkt und einer Korrosionsbeständigkeit gegenüber dem Milieu, ausgewählt aus nichtoxydierendem Stahl, Quecksilber, Kupfer und Blei, die Anode aus einem elektrisch leitenden und unter den Elektrolysebedingungen beständigen Material, wie Graphit, die Bezugselektrode aus gesättigtem Kalomel und die Trennmembran aus einem porösen Material, ausgewählt aus Sinterglas und lonenaustauschermembranen bestehen.
6. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß beim Arbeiten ohne Bezugselektrode die Stromdichte zu Beginn der Elektrolyse zwischen 0,5 und 2 Aldm2 beträgt.
7. Verfahren nach Anspruch 5, dadurch gekennzeichnet, daß beim Arbeiten mit einer Bezugselektrode das Potential der Kathode gegenüber der Bezugselektrode zwischen -0,25 und -0,55 Volt beträgt.
8. Verfahren nach einem der Ansprüche 5, 6 oder 7, dadurch gekennzeichnet, daß beim Arbeiten mit einer Trennmembran der Anodenraum einen Elektrolyten, ausgewählt aus den in der Säurebehandlungsstufe eingesetzten Säuren enthält.
9. Verfahren nach Anspruch 1,- dadurch gekennzeichnet, daß das metallische Rhodium an der Kathode in Form einer Ablagerung erhalten wird, die durch mechanisches Abschaben oder mittels Ultraschall entfernt wird.
EP19880400716 1987-03-25 1988-03-24 Elektrochemisches Verfahren zur Rückgewinnung von metallischem Rhodium aus wässerigen Lösungen von gebrauchten Katalysatoren Expired - Lifetime EP0288344B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT88400716T ATE55422T1 (de) 1987-03-25 1988-03-24 Elektrochemisches verfahren zur rueckgewinnung von metallischem rhodium aus waesserigen loesungen von gebrauchten katalysatoren.

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8704129 1987-03-25
FR8704129A FR2616810B1 (fr) 1987-03-25 1987-03-25 Procede electrochimique pour recuperer le rhodium metallique a partir de solutions aqueuses de catalyseurs usages

Publications (2)

Publication Number Publication Date
EP0288344A1 EP0288344A1 (de) 1988-10-26
EP0288344B1 true EP0288344B1 (de) 1990-08-08

Family

ID=9349402

Family Applications (1)

Application Number Title Priority Date Filing Date
EP19880400716 Expired - Lifetime EP0288344B1 (de) 1987-03-25 1988-03-24 Elektrochemisches Verfahren zur Rückgewinnung von metallischem Rhodium aus wässerigen Lösungen von gebrauchten Katalysatoren

Country Status (9)

Country Link
US (1) US4795538A (de)
EP (1) EP0288344B1 (de)
JP (1) JPS63259093A (de)
AT (1) ATE55422T1 (de)
CA (1) CA1308688C (de)
DE (1) DE3860411D1 (de)
ES (1) ES2016413B3 (de)
FR (1) FR2616810B1 (de)
GR (1) GR3000732T3 (de)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19804534C1 (de) * 1998-02-05 1999-06-24 Otb Oberflaechentechnik Berlin Verfahren zur elektrolytischen Regeneration verunreinigter Rhodiumlösungen

Families Citing this family (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CH672925A5 (de) * 1988-09-19 1990-01-15 Hana Dr Sc Nat Frauenknecht
GB9318794D0 (en) * 1993-09-10 1993-10-27 Ea Tech Ltd A high surface area cell for the recovery of metals from dilute solutions
FR2727637B1 (fr) * 1994-12-06 1997-01-03 Rhone Poulenc Chimie Procede de preparation electrochimique de catalyseurs a base de metal de transition et de phosphine
GB9806527D0 (en) 1998-03-26 1998-05-27 Bp Chem Int Ltd Process
JP3816241B2 (ja) 1998-07-14 2006-08-30 株式会社大和化成研究所 金属を還元析出させるための水溶液
US6764662B2 (en) * 2002-06-20 2004-07-20 Conocophillips Company Recover and recycle rhodium from spent partial oxidation catalysts
CN1875132A (zh) * 2003-09-16 2006-12-06 全球伊奥克斯有限公司 从溶液中去除物质的电解池
CN100564602C (zh) * 2006-07-05 2009-12-02 中国石油化工股份有限公司 一种氯铑酸的制备方法
CN101100756B (zh) * 2006-07-05 2010-07-07 中国石油化工股份有限公司 一种三氯化铑的制备方法
KR100858551B1 (ko) 2006-11-13 2008-09-25 진인수 전기화학적 방법에 의해 폐촉매로부터 백금족 금속을추출하는 방법

Family Cites Families (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4377450A (en) * 1982-04-15 1983-03-22 Bell Telephone Laboratories, Incorporated Palladium electroplating procedure
KR900001832B1 (ko) * 1985-04-25 1990-03-24 크로닌 엔지니어즈 코포레이션, 리미티드 귀금속의 용해 및 회수방법

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE19804534C1 (de) * 1998-02-05 1999-06-24 Otb Oberflaechentechnik Berlin Verfahren zur elektrolytischen Regeneration verunreinigter Rhodiumlösungen

Also Published As

Publication number Publication date
ATE55422T1 (de) 1990-08-15
FR2616810A1 (fr) 1988-12-23
DE3860411D1 (de) 1990-09-13
CA1308688C (fr) 1992-10-13
JPS63259093A (ja) 1988-10-26
GR3000732T3 (en) 1991-10-10
FR2616810B1 (fr) 1989-08-18
ES2016413B3 (es) 1990-11-01
EP0288344A1 (de) 1988-10-26
US4795538A (en) 1989-01-03

Similar Documents

Publication Publication Date Title
CN1102073C (zh) 回收抗坏血酸的电化学方法
EP0288344B1 (de) Elektrochemisches Verfahren zur Rückgewinnung von metallischem Rhodium aus wässerigen Lösungen von gebrauchten Katalysatoren
KR20130058678A (ko) 아릴-알킬 계면활성제 전구체의 전기화학 합성
EP0034544B1 (de) Verfahren zur Herstellung von Methionin
JPH0733595B2 (ja) 過マンガン酸塩へのマンガン酸塩の転化
RU2005117353A (ru) Способ электрохимического окисления ферроцианида до феррицианида
EP0117371B1 (de) Verfahren zur Herstellung von Aminobenzoesäuren aus entsprechenden Nitrotoluolen
US4582577A (en) Electrochemical carboxylation of p-isobutylacetophenone
EP0890566A1 (de) Oxidationsverfahren zur Herstellung einer Chlorobenzaldehyd
FR2546910A1 (fr) Procede de preparation de l'acide squarique par tetramerisation electrolytique de monoxyde de carbone dans du nitrile aliphatique anhydre comme solvant
CA1271490A (en) Oxidation of organic compounds using thallium ions
RU2135458C1 (ru) Способ получения янтарной кислоты
FR2582320A1 (fr) Procede electrochimique de preparation de derives organiques trifluoro (ou chlorodifluoro ou dichlorofluoro) methyles
KR890002864B1 (ko) m-히드록시벤질알코올의 제조방법
JP3806181B2 (ja) ナフタレンアルデヒド類の製造方法
US5466346A (en) Quinone synthesized from an aromatic compound in an undivided electrochemical cell
EP0267858B1 (de) Verfahren zur Herstellung von Vanadiumtrichlorid in wässriger Lösung
US5021132A (en) Electrochemical process for preparing 4,4'-dinitrostilbene-2,2'-disulfonic acid and the salts thereof
SU1664789A1 (ru) Способ получени п-аминометилбензойной кислоты
EP0436414A1 (de) Verfahren zur Herstellung von 2-amino-1,3-propandiol von seinen Salzen
EP0095206B2 (de) Verfahren zur Herstellung von 2,4,6-Trimethyl-4-hydroxycyclohex-2,5-dien-5-on
Genesty et al. Preparation of S 4 2-polysulfide from a sacrificial sulfur cathode and its use as a nucleophile in an electrochemically induced S RN 1 substitution reaction
EP0370920B1 (de) Verfahren zur Herstellung von Chinon aus Hydrochinon durch Elektrolyse
KR810001286B1 (ko) N-알킬피리디늄염의 전해 2량화법
FR2512844A1 (fr) Procede de preparation d'acides aminobenzoiques a partir des nitrotoluenes correspondants

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: RHONE-POULENC SANTE

17P Request for examination filed

Effective date: 19881128

17Q First examination report despatched

Effective date: 19900112

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AT BE CH DE ES FR GB GR IT LI LU NL SE

REF Corresponds to:

Ref document number: 55422

Country of ref document: AT

Date of ref document: 19900815

Kind code of ref document: T

ITF It: translation for a ep patent filed
GBT Gb: translation of ep patent filed (gb section 77(6)(a)/1977)
REF Corresponds to:

Ref document number: 3860411

Country of ref document: DE

Date of ref document: 19900913

REG Reference to a national code

Ref country code: GR

Ref legal event code: FG4A

Free format text: 3000732

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

26N No opposition filed
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: SE

Payment date: 19920203

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: BE

Payment date: 19920212

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: ES

Payment date: 19920214

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: LU

Payment date: 19920220

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 19920310

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GB

Payment date: 19920316

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: GR

Payment date: 19920324

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: AT

Payment date: 19920326

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: CH

Payment date: 19920327

Year of fee payment: 5

ITTA It: last paid annual fee
PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: NL

Payment date: 19920331

Year of fee payment: 5

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: DE

Payment date: 19920505

Year of fee payment: 5

EPTA Lu: last paid annual fee
PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19930324

Ref country code: GB

Effective date: 19930324

Ref country code: AT

Effective date: 19930324

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Effective date: 19930325

Ref country code: ES

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 19930325

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Effective date: 19930331

Ref country code: CH

Effective date: 19930331

Ref country code: BE

Effective date: 19930331

BERE Be: lapsed

Owner name: RHONE-POULENC SANTE

Effective date: 19930331

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: THE PATENT HAS BEEN ANNULLED BY A DECISION OF A NATIONAL AUTHORITY

Effective date: 19930930

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: NL

Effective date: 19931001

NLV4 Nl: lapsed or anulled due to non-payment of the annual fee
GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 19930324

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: FR

Effective date: 19931130

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: DE

Effective date: 19931201

REG Reference to a national code

Ref country code: FR

Ref legal event code: ST

REG Reference to a national code

Ref country code: GR

Ref legal event code: MM2A

Free format text: 3000732

EUG Se: european patent has lapsed

Ref document number: 88400716.2

Effective date: 19931008

REG Reference to a national code

Ref country code: ES

Ref legal event code: FD2A

Effective date: 19990405

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20050324